Aquacultural Engineering 4 (1985) 305-311

Short Communication Carbonate Mineral Filtrants with New Surfaces Reduce Alkalinity in Seawater and Artificial Seawater: Preliminary Findings

ABSTRACT Silica sand (silica), coral (aragonite ), and oyster shell (calcite) were ground to similar particle sizes and placed in seawater and artificial seawater (GP2 Medium). Alkalinity and pH values o f the artificial seawater decreased substantially over 24 h when in contact with coral and oyster shell; the effects in seawater were minor. Once alkalinity has been reduced, the maintenance o f stable pH at values typical o f seawater is made more difficult. The data, which are preliminary, have practical application.

INTRODUCTION The carbonate minerals aragonite, calcite, magnesian calcite and dolomite are c o m m o n l y used filtrants in the culture and maintenance o f marine organisms. These materials reportedly prevent the pH from declining to dangerously low levels. To serve as buffers in environments of "-pH 8 that become increasingly acidic, carbonate minerals would have to dissolve and contribute anions to the solution. Any buffering activity would be exhibited by a change in alkalinity, defined as the net negative charge o f all ions that interact with H . On nongeologic time scales the only species in seawater that make important contributions to the alkalinity are bicarbonate, carbonate, and borate. Contribution No. 42, Sea Research Foundation Inc. 305 Aquacultural Engineering 0144-8609/85/$03.30 - Elsevier Applied Science Publishers Ltd, England, 1985. Printed in Great Britain

306

G. Adams, S. Spotte

MATERIALS AND METHODS Seawater was collected in Long Island Sound off the southwestern tip of Fishers Island on an incoming tide. The water was vacuum-filtered aboard ship through 0.3 t~m sintered glass filters (Gelman, type AE, No. 61631, 47 mm). While at sea, the filtrate (~3 liters) was stored in a glass bottle kept on ice. Fresh seawater was collected and filtered before each trial. Salinity values were 32.0 to 33.0~oo both before and after the experiments, respectively. Artificial seawater was a single batch of GP2 Medium (Spotte et al., 1984) with trace ions (solutions C and D) excluded. This solution contains major ion concentrations typical of offshore seawater as reported by Brewer (1975). Salinity of the artificial seawater before the experiment was 36-0 to 37.5%o and measured 36.5 to 38.0%0 at the end. All solutions were refrigerated until immediately before use. Three filtrants were tested: silica sand, oyster shell, and coral. Oyster shell and coral were chosen because they represent different polymorphs of CaCO3 (calcite and aragonite, respectively). Silica sand contains no carbonates except as soluble surface precipitates. Sources were: silica sand (Ottawa Silica Co., Ledyard, Connecticut), crushed coral (Instant Ocean Hatcheries, Dade City, Florida), and crushed oyster shell (Agway, Westerly, Rhode Island). The mineral composition of each material was confirmed by X-ray power diffraction analysis. The silica sand was rinsed sequentially with 3 N HC1 and deionized water to remove surface carbonates. All materials were pulverized, ground in a stainless steel commercial blender, and sieved. Particles ranging from 212 to 500/.tm were collected, and lots of 1"0, 10-0 and 50-0 ml were weighed and stored in covered glass containers. Volume measure was used in an attempt to equalize the mineral surface areas. Temperature was measured with mercury thermometers to +0"5C. Salinity was measured with a hand-held, temperature-compensating refractometer (Aquafauna Bio-Marine, Hawthorne, California). Separate pH meters (Orion Model 701A, Orion Research Incorporated, Cambridge, Massachusetts) and electrode pairs (Orion 900200 doublejunction reference electrode coupled with an Orion 910100 glass pH electrode) were used to determine pH and alkalinity. The alkalinity procedure of Almgren and Fonselius (1976) was used. It requires plotting a calibration curve for a specific electrode pair; afterwards, no

Carbonate mineral filtrants and buffering

307

other electrode pair can be substituted. Both sets o f meters and electrode pairs were calibrated with NBS buffer standards o f pH 7 and 10. All trials were conducted at room temperature. In each trial 800 ml of seawater or GP2 Medium were poured into each o f four l-liter boiling flasks. The solutions were aerated through glass tubing at 940 ml rain -x for a minimum o f 12 h, which allowed the partial pressure of CO2 in the solutions to approach steady state and temperature to equilibrate at 21 C +- 1C. Volume flow o f air was regulated b y individual meters. A trial began when the test filtrant volumes of 1.0, 10.0 and 50-0 ml were transferred to the flasks containing the test solutions. Before starting a trial, the aeration tubing was removed and the flasks were swirled to dissolve salts from the sides. Volumes o f 500 ml from each flask were transferred to separate l-liter, three-neck, roundb o t t o m e d flasks. The glass electrode was placed in the left neck o f the flask, the reference electrode in the center, and the aeration tubing in the right neck, and the initial pH value was measured. Aeration continued for 24 h to stir the solutions and allow CO2 in the solution and air to approach equilibrium with atmospheric CO2. Subsequently the pH was measured in the flasks at 1, 2, 4, 8, and 24 h. The remaining 300 ml were used to determine time 0 values o f alkalinity and salinity. Alkalinity was always measured in triplicate. At 24 h some of the water was filtered through a 0.3/am sintered glass filter, and the final alkalinity and salinity were measured. Preliminary experiments using seawater and artificial seawater were conducted without filtrants to determine normal pH fluctuations in the control solutions.

RESULTS Alkalinity and pH measurements are shown in Table 1 and Fig. 1. Silica sand. The pH value changed by < 0.03 pH unit and the alkalinity by < 0 . 0 7 meq liter -x (2-4%) in all trials with silica sand in b o t h seawater and artificial seawater. Coral. The greatest pH change in seawater was a decrease o f 0-05 unit that occurred in the 50 ml sample. The greatest change in alkalinity, also observed in the 5 0 m l sample, was - - 0 . 1 9 m e q l i t e r -x or 11%. In artificial seawater the pH o f the 50 ml sample dropped by
-

308

G. Adams, S. Spotte
TABLE 1

Alkalinity and pH Data over 2 4 h for Three Volumes o f Filtrants Added to 500 ml of Seawater or Artificial Seawater. Alkalinity Data are Given as Means -+ Standard Deviations o f Triplicate Measurements

Filrrant

Vol.

Initial (0 h) pH Alk. (meq liter-1) l h

pH 2h 4h 8h

Final (24 h) pH Alk. [meq liter -1)

(mO

Seawater
Silica 0-00 1-00 10-00 50.0 0-00 1-00 10-00 50.00 0-00 1-00 10-00 50-00 8.04 8.02 8.03 8.04 8.04 8.06 8.06 8.06 8-08 8.09 8.08 8-09 1.86 -+ 0.01 1-92-+0-02 1-89-+ 0.01 1.91 -+ 0.01 1.95-+0.04 1.92-+ 0.00 1.93 +- 0.01 1-89 + 0.00 1.78-+ 0.02 1.74 -+ 0.03 1-78-+ 0-01 1.71 -+ 0.02 8.06 8.06 8.05 8.01 8-07 8.07 8-06 8.04 8-09 8.08 8.05 8.03 8.04 8.07 8.04 8.01 8.02 8.01 7.97 7.96 8.10 8-05 8.02 8.00 8-02 8-07 8-02 7.99 8.00 7-97 7.93 7.93 8.09 8-01 7.96 7.98 7.92 8.02 7.98 7-90 7.93 7-88 7.82 7-81 8-09 8-02 7-96 7.96 8.06 8.06 8-06 8.04 1.90 1.92 1.91 1-87 -+ 0-01 +-0.02 -+ 0-02 -+ 0.01

Oyster shell

8.10 1.97-+0-01 8.09 1.94-+ 0-01 8-08 1-90-+ 0.01 8.05 1-75 -+ 0.01 8.09 8.09 8.06 8.03 1-85 +- 0-00 1.78 --- 0.00 1-69-+ 0.01 1.52-+ 0.01

Coral

Artificial seawater
Silica 0-00 1-00 10.00 50.00 0.00 1-00 10.00 50-00 0-00 1.00 10.00 50-00 50-00 8.13 8.12 8.13 8.13 8.14 8-14 8-14 8-14 8.12 8.14 8.14 8.14 2.59+-0.02 2.51 -+0.03 2-55 +-0.02 2.50+- 0.02 2.38 2.35 2.37 2.47 -+ 0.05 + 0-01 +- 0-01 +- 0-01 8.15 8.14 8-13 8-10 8.14 8-14 8-12 8.10 8.14 8.13 8.08 8.00 8-17 8-15 8.14 8.12 8-14 8.14 8.10 8-09 8-15 8-13 8.07 7.99 8.16 8.15 8.10 8.12 8.14 8-15 8-07 8-10 8.12 8-10 8-03 7.95 8.12 8-06 8.04 8.06 8-10 8.09 8-03 8-04 8-16 8.14 8.01 7.95 8-15 8-15 8.14 8.14 2.64+-0.01 2.58-+ 0.02 2.59 + 0.02 2.48+- 0-01

Oyster shell

8.10 2.46 +- 0.02 8-09 2.33 -+ 0.02 8.05 2.01 +- 0-02 8-02 1-76-+ 0.01 8.16 2.54 +- 0.00 8.13 2.29-+ 0-01 8.00 14.9-+0.02 7-93 1.33 +- 0.02 1.21 +- 0.02 a

Coral

2.55 +- 0-01 2.52 +0-01 2.53+-0-00 2-46-+ 0.01 2-32 -+ 0.03 a

a Data for a repeated trial (see text).

Carbonate mineral filtrants and buffering

o 2.5

309

Seawater

- silica

GP2 Medium - silica 5o

t~

2.0-

|
< 1.5-

e1110 50

Seawater
2.5

- coral

GP2 Medium - coral

rt S
2.0

1.5 i

so,/

/ so I i
5l I

io
I

Seawater
2.5

- oyster shell

GP2 Medium - oyster shell o

~r 2.0

~o~
t < 1.5

I 8.0

I 8.1

I 8.2

I 8.0

I 8.1

I 8.2

pit

mt

Fig. 1.

Plot of alkalinity and pH of seawater and artificial seawater (GP2 Medium)

24 h after addition of filtrants. Closed circles represent conditions at the start. Arrowheads indicate conditions after 24 h. Numbers represent the volume of a filtrant (in ml) added. Dashed line is a repeated trial.

0-21 unit, and alkalinity dropped by 1-13 meq liter -1 o r - - 4 6 % . The change in the 50 ml sample seemed inordinately great, and this part of the experiment was repeated 2 weeks later using a different batch of artificial seawater. Results were similar. The pH again decreased by 0"21 unit. Alkalinity decreased 1"11 meq liter -1 (--48%), compared with the initial value o f a decrease o f 1"13 meq liter -x.

310

G. Adams, S. Spotte

Oyster shell. The greatest change in pH in seawater samples was +0.05 unit, whereas the pH of the 50 ml sample in artificial seawater changed by --0.21 unit. The alkalinity changes in the seawater samples were small except in the 50 ml sample which decreased by 0.14 meq liter -~ or 7%. The alkalinity of the artificial seawater decreased by 0.71 meq liter -1 or 29% in the 50 ml sample.

DISCUSSION Seawaters in the mixed layer of temperate and tropical oceans are typically supersaturated with calcite and aragonite (Berner, 1974), and a high degree of supersaturation is required before a perceptible rate of calcite precipitation can be established on carbonate mineral surfaces (Berner, 1975). The seawater and artificial seawater used in our experiments were supersaturated with respect to both aragonate and calcite. The ion products in each case, as compared with solubility measurements in Table 3 of Mucci (1983), were: aragonite 150%, calcite 260% (seawater), and aragonite 270%, calcite 275% (artificial seawater). All trials seemed poised to lose CaCO3 by precipitation upon introduction of suitable surfaces. In an experiment similar to ours Wollast et al. (1980) added reagent grade calcite to a system closed to the atmosphere. When the system was opened the following reaction occurred:
C a 2+ + 2HCO3- = CaCOa(s) + CO2 + H20

as CO2 was swept out, the concentration of CO~- increased, and additional CaCO3 precipitated. Moles of CO2 driven into the atmosphere were equal to moles of CO32- precipitated. The loss of alkalinity we observed is consistent with this reaction because CO~- was lost. In qualitative terms our preliminary findings can be summarized this way. Silica had no discernible affect on alkalinity and pH in either seawater or artificial seawater. In the case of alkalinity the magnitude of the changes were similar to the standard deviations of the measurements. Addition of a carbonate mineral in all situations reduced the alkalinity and pH of seawater and artificial seawater, but the reductions in artificial seawater were consistently greater. In both solutions larger additions of filtrant (i.e. larger solid-to-solution ratios) resulted in greater reductions in alkalinity and pH. Decreases in both factors were always greater with coral than oyster shell.

Carbonate mineral filtrants and buffering

311

When new carbonate filtrants are placed in contact with seawater and artificial seawater alkalinity is lost rapidly, pH declines, and the concentrations o f calcium and magnesium are altered. To help minimize these changes we recommend that new filtrants be soaked in seawater or artificial seawater for at least 24 h prior to use. Afterward, the solution should be discarded. The alternative o f adding sufficient sodium bicarbonate to counteract the reduction in alkalinity will not prevent the initial loss o f cations.

ACKNOWLEDGEMENTS The manuscript was reviewed by James W. Atz, Joseph P. Bidwell, John D. Buck, Robert L. Jenkins, and Richard M. Segedi. Patricia M. Bubucis provided technical assistance.

REFERENCES Almgren, T. & Fonselius, S. H. (1976). Determination of alkalinity and total carbonate. In: Methods of Seawater Analysis, ed. K. Grasshoff, Verlag Chemic, Weinheim, pp. 97-115. Berner, R. A. (1974). Physical chemistry of carbonates in the oceans. In: Studies in Paleo-Oceanography, ed. W. H. Hay, SEPM, Tulsa, pp. 37-43. Berner, R. A. (1975). The role of magnesium in the crystal growth of calcite and aragonite from sea water. Geochim. Cosmochim. Acta, 39,489-504. Mucci, A. (1983). The solubility of calcite and aragonite in seawater at various salinities, temperatures, and one atmosphere total pressure. Am. J. Sci., 283, 780-99. Spotte, S., Adams, G. & Bubucis, P. M. (1984). GP2 Medium is an artificial seawater for culture or maintenance of marine organisms. Zoo Biol., 3,229-40. Wollast, R., Garrels, R. M. & Mackenzie, F. T. (1980). Calcite-seawater reactions in ocean surface waters. Am. J. Sci., 280, 831-48.

Gary Adams and Stephen Spotte

Mystic Marinelife Aquarium, Sea Research Foundation Inc., Mystic C T 06355, USA